CN101077964B - method for producing polyether polyols - Google Patents
method for producing polyether polyols Download PDFInfo
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- CN101077964B CN101077964B CN2007101040858A CN200710104085A CN101077964B CN 101077964 B CN101077964 B CN 101077964B CN 2007101040858 A CN2007101040858 A CN 2007101040858A CN 200710104085 A CN200710104085 A CN 200710104085A CN 101077964 B CN101077964 B CN 101077964B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
- B01J27/26—Cyanides
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4866—Polyethers having a low unsaturation value
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/08—Saturated oxiranes
- C08G65/10—Saturated oxiranes characterised by the catalysts used
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/08—Saturated oxiranes
- C08G65/10—Saturated oxiranes characterised by the catalysts used
- C08G65/12—Saturated oxiranes characterised by the catalysts used containing organo-metallic compounds or metal hydrides
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2663—Metal cyanide catalysts, i.e. DMC's
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- C08G2190/00—Compositions for sealing or packing joints
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S521/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S521/914—Polyurethane cellular product formed from a polyol which has been derived from at least two 1,2 epoxides as reactants
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Abstract
The invention relates to a method for conditioning double metal cyanide ('DMC') catalysts for producing polyether polyols from starter compounds having active hydrogen atoms, to a method for producing polyether polyols using the conditioned catalysts, and to the use of the polyether polyols produced in this way for producing polyurethane materials.
Description
Technical field
The invention provides the method for a kind of adjusting (conditioning) DMC catalysts (" dmc catalyst "), this catalyzer is used for preparing polyether glycol by the initial compounds with active hydrogen atom, the invention still further relates to the method for using the Preparation of Catalyst polyether glycol of regulating, and the application of the polyether glycol of preparation in this manner in the preparation polyurethane material.
Background technology
Can obtain being applicable to the polyether glycol of preparation polyurethane material by various preparation method.On the one hand, the epoxy alkane base catalysis adds on the initial compounds with Zerewitinoff active hydrogen atom, on the other hand, use double metal cyanide epoxy alkane to be added on the initial compounds with Zerewitinoff active hydrogen atom as catalyzer, this two aspect is significant in large-scale commercial production.The importance that epoxy alkane (Louis) acid catalysis adds on the suitable initial compounds is lower.
Epoxy alkane (for example, oxyethane or propylene oxide) base catalysis at alkali metal hydroxide, alkalimetal hydride or amine (for example adds on the initial compounds with Zerewitinoff active hydrogen atom, N, N-dimethyl benzylamine or imidazoles) carry out under existing.After the addition of epoxy alkane takes place, necessary with in inorganic diluted acid (for example, sulfuric acid or phosphoric acid) or the organic acid (for example lactic acid) and the polymerization activity center on the polyether chain.If suitable, formed salt must separate to be removed.Can also utilize acidic silicic acid salt thin slice or acid cation-exchanger to handle alkaline polymer.In the catalytic epoxy alkane addition reaction of amine,, then can omit further processing if the amine that exists in these polyether glycols can not damage the preparation of polyurethane material.Except must handling polyether glycol,, as before the polyurethane component, notice that the epoxy alkane base catalysis adds to and has two other shortcomings on the initial compounds with Zerewitinoff active hydrogen atom at polyether glycol if suitable.Can only obtain the lower polyethers of equivalent weight by amine catalyst, referring to for example Ionescu etc. at " Advances in Urethane Science﹠amp; Technology ", 1998,14, described in the 151-218 page or leaf.Under alkali metal hydroxide catalysis, along with the increase of polymkeric substance molar mass, disadvantageous side reaction obviously increases.Here pay particular attention to, the vinyl carbinol of propylene oxide isomerization for having high equivalent weight weight (or low OH value) causes the content of monofunctional polyethers material in the reaction mixture higher.The monofunctional polyethers molecule can cause disadvantageous effect to the completely solidified character and the change in physical curve of polyurethane system.
Use DMC catalysts, can accelerate epoxy alkane (particularly propylene oxide) and add to the speed that reaches low-down OH value on the initial compounds with Zerewitinoff active hydrogen atom, and not have the above-mentioned propylene oxide isomerization of discernable degree be that the situation of vinyl carbinol takes place.For example, the high reactivity dmc catalyst of describing in US-A5470813, EP-A 700949, EP-A 743093, EP-A 761708, WO 97/40086, WO98/16310 and WO 00/47649 also has very high activity, can prepare polyether glycol down at low-down catalyst concn (being equal to or less than 25ppm), therefore no longer need from end product, to separate and remove catalyzer.Typical example is the high reactivity dmc catalyst of describing among the EP-A 700949, this catalyzer is except (for example containing double metal cyanide, six cyano group cobalt acid (III) zinc) and outside the organic complex part (for example, the trimethyl carbinol), also contain the polyethers of number-average molecular weight greater than 500 gram/moles.
The feature of dmc catalyst be them for by for example a large amount of initial compounds (such as, ethylene glycol, propylene glycol, glycerol, TriMethylolPropane(TMP), Sorbitol Powder or sucrose) and reaction mixture in the hydroxyl high density that causes of polar impurity have outstanding susceptibility.At the reaction initial period, dmc catalyst can not be converted into the polymerization activity form.Impurity can be, for example, water has the compound (for example carbohydrate and carbohydrate derivates) of a plurality of next-door neighbours' hydroxyl or has the compound (for example, amine) of basic group.Have the material that is close to carbonyl or has the carbonyl adjacent and also can cause disadvantageous effect catalyst activity with hydroxyl.Yet, in order to use initial compounds or to have the initial compounds of the impurity of the catalyst posions that is considered to the catalytic epoxy alkane addition reaction of DMC, must reduce hydroxyl concentration with high density OH base, perhaps make catalyst posions harmless.For this purpose, the past at first prepares prepolymer by these initial compounds by base-catalyzed method, after fully handling, can these prepolymers be converted into the epoxy alkane adduct of required high molecular weight by DMC catalysis.Another important progress has been to develop the continuous measurement of initial compounds in this respect, has disclosed this point among the WO97/29146.In this case, crucial initial compounds is not to join in the reactor at the very start, but joins in the reactor continuously with epoxy alkane in reaction process.In this method, at first the starting medium of prepolymer as reaction joined in the reactor, the product itself that can also use a small amount of preparation is as starting medium.In a kind of preparation process in back, the step that must prepare the prepolymer that is applicable to further epoxy alkane addition at first separately can be omitted.But, if obtain the short-chain polyethers alcohol of OH value, then need to improve the ratio of separating out initial compounds and epoxy alkane in the logistics that is metered into greater than 200 milligrams of KOH/ gram, so still exist hydroxyl and polar impurity to reach the danger of threshold concentration.In this class situation, catalyzer is metered into stage loss of activity gradually at initial compounds, and this confirms by following phenomenon itself: because the concentration increase of free epoxy alkane causes the reactor pressure rising.
If use the transformable compound of purity (for example compound that is made by renewable raw materials) as initial compounds, then Wei Zhi accessory constituent can damage catalyst activity equally significantly.In this case, catalyzer can not be converted into activity form at all, can not observe above-mentioned catalyst activity forfeiture.
On the one hand, improve catalyst concn and certainly eliminate the problems referred to above, on the other hand, also can remove impurity in the initial compounds, for example carry out abundant stripping, distillation or extraction in the temperature that is higher than 80 ℃ by appropriate pretreatment.All these selections all are the costs that spends again consuming time.
Summary of the invention
Therefore, the invention provides a kind of method of handling dmc catalyst, this method can be carried out the process that the initial compounds continuous measurement adds with higher initial compounds and epoxy alkane ratio, therefore can use the OH value can not go wrong, promptly not need the initial compounds that initially joins the starting medium in the reactor or be metered into is carried out pre-treatment greater than the polyether glycol of 200 milligrams of KOH/ grams.In addition, the meeting that makes catalyzer can resist any kind consumingly of this method hinders the disadvantageous effect that catalyzer is converted into the impurity of polymerization activity form.This class impurity for example can be present in the initial compounds that the renewable resources by raw material obtains.
Embodiment
To the present invention be described unrestricted purpose for explanation now.Unless in work embodiment, indication is arranged in addition perhaps, the numeral of all expression quantity, percentage ratio, OH value, functionality etc. all is interpreted as using in all cases " pact " to modify in the specification sheets.Unless indication is arranged in addition, equivalent weight that provides with dalton (Da) in the literary composition and molecular weight are respectively number average equivalent weight and number-average molecular weight.
The invention provides the method for a kind of adjusting double metal cyanide (DMC) catalyzer, wherein, in 5 minutes to 4 hours, preferred 15 minutes to 2 hours time, pressure be 1 millibar to 10 the crust inert gas atmospheres under, temperature at 0-80 ℃, preferred 20-60 ℃, these catalyzer be dispersed in precursor or the polyether glycol of the reaction product that is equivalent to prepare in, described precursor is as the starting medium of alkoxylation, OH value is that 5-500 milligram KOH/ restrains.Be called in the text in this preprocessing process of " adjusting ", may have epoxy alkane, for example propylene oxide and/or oxyethane.Carry out if be adjusted under the epoxy alkane existence, then the actual activation of catalyzer did not begin as yet in this adjusting stage, and the pressure decline that the catalyst activation effect begins to show as in the reactor is accelerated.
The present invention also provides a kind of method for preparing polyether glycol, wherein uses the catalyzer of regulating according to the present invention, and the application of the polyether glycol of preparation in this manner in the preparation polyurethane material.
OH value with the polyether glycol of the Preparation of Catalyst through overregulating is a 5-500 milligram KOH/ gram.Catalyst concentration is generally 10-1000ppm in the end product.The notable feature of the dmc catalyst through overregulating is to have high catalytic activity, and all keeps this high catalytic activity in entire reaction course.When method of the present invention is carried out, under the identical situation of other method parameter, low during obviously than the method for using prior art as the dividing potential drop that produces by unreacted epoxy alkane of the indication of catalyst activity.Therefore, in this manner can also obvious raising method reliability.
Carry out according to following details according to method of the present invention: at first the precursor of a small amount of OH value for 5-500 milligram KOH/ gram joined in the reactor under inert atmosphere (for example nitrogen or rare gas) as starting medium.The amount of the suitable precursor that uses as starting medium depends on concrete reactor and agitator geometric construction and heating and cooling Design of device.Should be selected, make reaction mixture be stirred easily, and the material that reaction heat is removed easily or reactor is interior is heated easily.The OH value is that all cpds of 5-500 milligram KOH/ gram can be used as precursor.Preferred precursor is for example to have the lower molecular weight initial compounds of Zerewitinoff active hydrogen atom and the adduct of epoxy alkane, polyester polyol or polycarbonate polyol and hydroxylated tri-glyceride or hydroxylated derivative of fatty acid.If this method is undertaken by the method that continuous measurement adds initial compounds, then a small amount of product batch of material of preparation earlier itself is commonly used for starting medium.Because under 0-80 ℃ temperature, carry out, so suit before catalyzer adds, by for example remove the water of trace in the starting medium with nitrogen or rare gas element stripping in the temperature that is higher than 80 ℃ according to catalyzer regulate process of the present invention.The ceiling temperature that is applicable to the temperature range of this process is only limited by the thermodynamic stability of starting medium.
And, can add the inert organic solvents of toluene and/or THF and so on, to reduce the viscosity of starting medium.Total amount in batch of material is a benchmark, and the amount of solvent is generally 10 weight % to 30 weight % in this class situation.This method is preferably carried out under the situation of solvent not having.
Dmc catalyst is joined in the starting medium.The catalyst concn that calculates with respect to the amount of end product is 10-1000ppm.In the amount of used starting medium is that a small amount of epoxy alkane of the maximum 20 weight % of benchmark has joined in the starting medium that contains catalyzer, and these epoxy alkane have preferably been handled by stripping with rare gas element at 0-80 ℃ and carried out drying.
The adjusting of catalyzer, by catalyzer was disperseed in starting medium 5 minutes to 4 hours, was carried out under preferred 20 ℃ to the 60 ℃ temperature preferably at 0 ℃ to 80 ℃ in preferred 15 minutes to 2 hours.Preferably the starting medium that contains catalyzer by stirring disperses.Agitator speed is preferably 40-800rpm.The pumping that can also circulate contains the starting mixt of catalyzer, uses static mixer or jet spread device, perhaps disperses by ultrasonic.If also be not metered into easy evaporable epoxy alkane, can also remove low molecular weight impurities (as water) in the starting medium by discharging and/or rare gas element stripping at conditioning period.Stripping or discharging were preferably carried out 15-60 minute.
By be heated to 80-160 ℃, preferred 100-140 ℃, preferred 120-140 ℃ temperature is come deactivated catalyst especially.For this process, will be that the epoxy alkane of benchmark 5-20 weight % joins in the reactor in the amount of starting medium, prerequisite is that this operates in the adjusting stage and did not carry out.Can be before the material in the reactor be heated to activation temperature, during or add epoxy alkane afterwards.The activation of catalyzer is accelerated to confirm by the decline of reactor pressure, shows that thus epoxy alkane begins to transform.The epoxy alkane or the epoxy alkane mixture of aequum can be joined in the reaction mixture continuously then, the temperature of reaction of selection is 20-200 ℃, but is preferably 50-160 ℃.Especially preferably with activation temperature as temperature of reaction.
If another part initial compounds or initial compounds mixture are joined in the reactor by the method for continuous measurement adding initial compounds, when the amount in starting medium is a benchmark when having had the epoxy alkane of 10-60 weight % or epoxy alkane mixture to join in the starting medium, begin to add above-mentioned another part initial compounds or initial compounds mixture.The speed that is metered into of another part initial compounds or initial compounds mixture is preferably after being metered into initial compounds (mixture) end, can also be metered into a small amount of epoxy alkane (mixture) again to reach required OH value.But, can also make to be metered into initial compounds (mixture) and epoxy alkane (mixture) finishes simultaneously.
In the another kind of form of preparation polyether glycol, the whole initial compounds that are used for preparing polyether glycol are in the process of regulating dmc catalyst Already in the starting medium.Has only still continuous measurement adding behind catalyst activation of epoxy alkane (mixture).
After being metered into epoxy alkane (mixture) end, then be the reaction latter stage, wherein preferably quantize the density loss of unreacted epoxy alkane by adjusting pressure.When pressure is constant, product is randomly discharged from reactor after an abundant heating phase.
As the WO 98/03571 described method for preparing polyether glycol fully continuously also is important selectable method.In this method, catalyzer must join in the reactor continuously with epoxy alkane and starting mixt.For this purpose, by above-mentioned catalyzer control method, preparation contains the dense dispersion of the catalyzer through overregulating of 0.1-10 weight % in the presence of no epoxy alkane, adds in the reactor in totally continuous polyether glycol preparation process then.
The dmc catalyst that is applicable to the inventive method in principle is known.As what mentioned, dmc catalyst is main be used for by the epoxy alkane addition polymerization is prepared to the initial compounds with active hydrogen atom polyether glycol (referring to, for example US-A 3404109, US-A 3829505, US-A 3941849 and US-A 5158922), this is because compare with the ordinary method of using alkaline catalysts to prepare polyether glycol, uses dmc catalyst can reduce the content of the monofunctional polyethers (being called single alcohol (mono-ols)) with terminal double link.And alkali susceptibility functional group such as carbonyl functional group or ester group can be kept perfectly in the catalytic epoxy alkane addition reaction of DMC.And, also has very high activity as the improved dmc catalyst described among US-A 5470813, EP-A 700949, EP-A 743093, EP-A 761708, WO 97/40086, WO 98/16310 and the WO 00/47649 as mentioned above, can be at the following preparation polyether glycol of low-down catalyst concn (being equal to or less than 25ppm), therefore no longer need catalyzer separated from end product and remove.Example comprises the high reactivity dmc catalyst of describing among the EP-A 700949, wherein also contains polyethers and double metal cyanide (for example, six cyano group cobalt acid (III) zinc) and the organic complex part (for example, the trimethyl carbinol) of number-average molecular weight greater than 500 gram/moles.
Suitable epoxy alkane is for example oxyethane, propylene oxide, 1,2-and 2,3-butylene oxide ring and Styrene oxide 98min..What preferably use is propylene oxide and oxyethane, and they use separately or use as mixture.If use several different epoxy alkane, then they can be used as mixture or one after the other are metered into.In a kind of situation about being metered in back, polyether chain has block structure.But, in order to obtain specified block structure in the methods of the invention, need be when finishing to be metered into the first epoxy alkane block or before finish initial compounds soon continuous measurement add.Preferably, the propylene oxide that pure ethylene oxide or ethylene oxide content is higher and the mixture of oxyethane are metered into as end-blocks, and Zhi Bei polyether glycol contains the uncle OH end group of 40-100% like this.
Can be for example lactone, lactide, acid anhydrides, cyclic carbonate ester and carbonic acid gas by other monomer of this method and epoxy alkane copolymerization.Their use has been described among US-A 3538043, US-A 4500704, US-A 5032671 and the US-A6646100.
Be applicable to that the preferred functionality of initial compounds that the continuous initial compounds that uses the dmc catalyst of regulating according to the present invention is metered into method is 2-8.Example is propylene glycol, ethylene glycol, glycol ether, 1,2-butyleneglycol, 1,3-butyleneglycol, 1,4-butyleneglycol, hexylene glycol, pentanediol, 3-methyl isophthalic acid, 5-pentanediol, 1,12-dodecanediol, glycerol, TriMethylolPropane(TMP), trolamine, tetramethylolmethane, Sorbitol Powder, sucrose, quinhydrones, pyrocatechol, resorcin(ol), Bisphenol F, dihydroxyphenyl propane, 1,3,5-trihydroxybenzene, formaldehyde and phenol or contain the melamine of methylol or the condensation product and the Mannich base of urea.Monoamine or the polyamines that can choose use wantonly are quadrols, 1,3-diaminopropanes, 1,4-diaminobutane, 1, the isomer of the isomer of 6-hexanediamine, thanomin, diethanolamine, diethylenetriamine, aniline, piperazine, tolylene diamine and (diamino-diphenyl) methane.Preferred use does not contain amino initial compounds.
Polyester polyol also is suitable as the initial compounds that continuous measurement adds or joins starting medium in the reaction vessel at the beginning.These polyester polyols can be by organic dicarboxylic acid that for example has the 2-12 carbon atom and polyvalent alcohol (preferred diol) preparation with 2-12 carbon atom (preferred 2-6 carbon atom).Operable dicarboxylic acid for example is: Succinic Acid, pentanedioic acid, hexanodioic acid, suberic acid, nonane diacid, sebacic acid, decane dicarboxylic acid, dodecanedicarboxylic acid, toxilic acid, fumaric acid, phthalic acid, m-phthalic acid and terephthalic acid.In this case, dicarboxylic acid can use separately or use as mixture.Except free dicarboxylic acid, can also use corresponding dicarboxylic acid derivatives, for example have dicarboxylic acid monoesters and/or the dicarboxylic diester or the dicarboxylic anhydride of the alcohol of 1-4 carbon atom.Preferred usage ratio is the dicarboxylic acid mixture of Succinic Acid, pentanedioic acid and the hexanodioic acid of 20-35/40-60/20-36 weight part, especially preferably uses hexanodioic acid.The example of dibasic alcohol and polyvalent alcohol is ethylene glycol, glycol ether, 1,2-and 1, ammediol, dipropylene glycol, methyl isophthalic acid, ammediol, 1,4-butyleneglycol, 1,5-pentanediol, 3-methyl isophthalic acid, 5-pentanediol, 1,6-hexylene glycol, neopentyl glycol, decamethylene-glycol, 1,12-dodecanediol, glycerol, TriMethylolPropane(TMP) and tetramethylolmethane.Preferred 1, glycol ether, 1, the 4-butyleneglycol, 1 of using, the mixture of 6-hexylene glycol, glycerol, TriMethylolPropane(TMP) or above-mentioned at least two kinds of glycol, especially preferably make spent glycol, 1,4-butyleneglycol and 1, the mixture of 6-hexylene glycol, glycerol and/or TriMethylolPropane(TMP).Can also use the polyester polyol that obtains by lactone (for example 6-caprolactone) or hydroxycarboxylic acid (for example hydroxycaproic acid and oxyacetic acid).
In order to prepare this kind polyester polyvalent alcohol, organic aromatics or aliphatic polycarboxylic acid and/or polycarboxylic acid derivative and polyvalent alcohol can not use catalyzer or in the presence of esterifying catalyst, advantageously (for example at rare gas element, nitrogen, helium or argon gas) in, and under the temperature of 150-300 ℃ (preferred 180-230 ℃) as melt, randomly under reduced pressure carry out polycondensation, up to reaching required acid number and OH value.Acid number is preferably less than 10 milligrams of KOH/ grams, preferably less than 2.5 milligrams of KOH/ grams.
In a kind of preferred manufacturing procedure, esterification mixture earlier at normal pressure, carries out polycondensation then under the pressure less than 500 millibars (preferred 1-150 millibars) under said temperature, make acid number reach 80-30, is preferably 40-30.Operable esterifying catalyst is iron, cadmium, cobalt, lead, zinc, antimony, magnesium, titanium and the tin catalyst of for example metal, metal oxide or metallic salt form.But the polycondensation of aromatics or aliphatic carboxylic acid and polyvalent alcohol also can be carried out under thinner and/or entrainment agent effect in liquid phase, and thinner and/or entrainment agent are for example benzene,toluene,xylene or chlorobenzene, are used for removing condensation water by component distillation.
Select the ratio of di-carboxylic acid (derivative) and polyvalent alcohol,, can determine the functionality of selected alcohol according to simple method well known by persons skilled in the art to obtain required OH value, functionality and viscosity.
The polycarbonate that contains hydroxyl also is suitable as the initial compounds that continuous measurement adds or joins starting medium in the reaction vessel at the beginning.The polycarbonate of operable hydroxyl be itself known can be by glycol as 1,2-propylene glycol, 1,4-butyleneglycol, 1, those types that 6-hexylene glycol, glycol ether, triglycol, the low polytetramethylene glycol of Tetraglycol 99 and/or oligomeric hexamethylene glycol and diaryl carbonate and/or dialkyl carbonate such as diphenyl carbonate, methylcarbonate and α-ω-bischloroformate or phosgene reaction prepare.
Be applicable to that in preparation importance in the polyvalent alcohol of polyurethane industrial is in continuous increase in order to overcome the unfavorable grade of fossil feedstock in the situation that petroleum resources lack and the eubiosis, use the raw material that obtains by renewable resources.A kind of method that can be used for preparing this class polyvalent alcohol is that epoxy alkane is added on the hydroxylated tri-glyceride, for example hydroxylated soya-bean oil or hydroxylated rape seed oil.This class initial compounds can be particularly advantageously by method of the present invention and epoxy alkane reaction.Other derivative of fatty acid such as lipid acid mono alkyl ester can certainly and be used for method of the present invention by hydroxylation.Hydroxylated tri-glyceride and/or hydroxylated derivative of fatty acid can join in the reaction vessel as starting medium at the beginning, perhaps are metered into the stage at epoxy alkane and join in the reactor continuously as initial compounds.
All initial compounds or starting medium can use separately or use as mixture.And, described in WO 99/14258, can in initial compounds and/or starting medium, add the organic acid or the mineral acid of a small amount of (1-500ppm).
A key character of the present invention is to reduce the susceptibility of dmc catalyst to polytype impurity in initial compounds (mixture) or the starting medium by regulating.Therefore, the purification process to initial compounds (mixture) or starting medium that relates to can be reduced to a minimum in most of situation, perhaps avoids fully.For example, though very high in the ratio of separating out initial compounds in the logistics (mixture) and epoxy alkane that is metered into, dmc catalyst can be especially not sensitively yet with initial compounds (mixture) in the water reaction; Even the low dividing potential drop of epoxy alkane has confirmed high catalyst activity stable when lower catalytic amount in reaction process.
Antiaging agent such as antioxidant can randomly join in the polyvalent alcohol that obtains by the inventive method.
Polyvalent alcohol itself can or randomly as mixture and other isocyanate-reactive component, with organic multiple isocyanate, randomly in the presence of whipping agent, in the presence of catalyzer, randomly with other additive (for example, foaming stabilizer) reaction is in this way as the component of solid or foamed polyurethane material.
Embodiment
The raw material that uses
The catalyzer (dmc catalyst) that is used for the epoxy alkane addition:
By six cyano group cobalts acid zinc, the trimethyl carbinol and number-average molecular weight is that the polypropylene glycol of 1000 gram/moles prepares DMC catalysts; Described in EP-A 700949
Polyvalent alcohol A
Trifunctional polyethers, OH value are 238, are added on the glycerol by propylene oxide to obtain.
Polyvalent alcohol B
Two functional polyethers, OH value are 260, are added on the propylene glycol by propylene oxide to obtain.
Polyvalent alcohol C
Trifunctional polyethers, OH value are 56, are added on the glycerol by propylene oxide to obtain.Polyvalent alcohol C contains the phosphoric acid of 200ppm.
The preparation of hydroxylated rape seed oil (polyvalent alcohol D)
Under nitrogen atmosphere, restrain the rape seed oil (content of erucic acid: 0.3 weight % that obtains by the 00-vegetable seeds with 3050, free fatty acid content: 0.6 weight %, iodine number: 117 gram iodine/100 grams, obtain from the Campa Biodiesel of German Ochsenfurt) at first join the glass flask, be heated to 70 ℃.In each situation, 370.4 gram formic acid and 457.7 were restrained hydrogen peroxide (aqueous solution, concentration are 50%) in 7 hours, be divided into 7 equal portions by two dropping funnels and add.After the formic acid part, directly be metered into the hydrogen peroxide part.After in the end a part adds, reaction mixture was kept 1 hour at 70 ℃ after reaction, then reflux temperature (105 ℃) heating 4 hours.The oxygen level of oxyethane (oxirane) is 0.051 weight %.Behind dephlegmate and unreacted formic acid, product under 1 millibar pressure, was fully heated 3 hours at 110 ℃.The OH value of hydroxylated rape seed oil is 149.8 milligrams of KOH/ grams, and its acid number is 5.63 milligrams of KOH/ grams.
Embodiment 1
0.39 gram dmc catalyst is joined among the gram of 750 in the 10 liters of autoclaves polyvalent alcohol A.Then the material in the reactor is heated to 60 ℃, stripping 30 minutes stirs (450rpm) and logical nitrogen (50 ml/min) simultaneously.Then under 100 millibars, with the material in the reactor 60 ℃ of restir 60 minutes.Then, with mixture heating up to 130 ℃, add 80 gram propylene oxide with the metering rate of 200 Grams Per Hours in reactor, pressure is elevated to 1.2 crust.The pressure lowering speed is accelerated to show that dmc catalyst activates subsequently.Behind catalyst activation, in autoclave, be metered into another part 4484.8 gram propylene oxide with the speed of 1087 stable Grams Per Hours.After being metered into totally 100 gram propylene oxide (comprising the amount that catalyst activation is used), begin to be metered into 46 gram propylene glycol (containing 750ppm water) with stable metering rate 22.75 Grams Per Hours.After being metered into totally 250 gram propylene oxide (comprising the amount that catalyst activation is used), begin to be metered into 639.3 gram glycerol (containing 2000ppm water and 75ppm phosphoric acid) with stable metering rate 177.5 Grams Per Hours.After being metered into the propylene oxide end, mixture was kept 23 minutes at 130 ℃ after reaction again, with product in a vacuum, fully heated 30 minutes at 130 ℃.The maximum loop Ethylene Oxide dividing potential drop of the difference decision between the stress level that reaches when being finished by maximum reactor pressure and reaction latter stage is 1.4 crust.The OH value of product is 235.3 milligrams of KOH/ grams.
Embodiment 2
0.39 gram dmc catalyst is joined among the gram of 750.9 in the 10 liters of autoclaves polyvalent alcohol A.Then the material in the reactor is heated to 60 ℃, stripping 30 minutes stirs (450rpm) and logical nitrogen (50 ml/min) simultaneously.Then under 100 millibars, with the material in the reactor 60 ℃ of restir 30 minutes.Then, with mixture heating up to 130 ℃, add 80 gram propylene oxide with the metering rate of 250 Grams Per Hours in reactor, pressure is elevated to 1.2 crust.The pressure lowering speed is accelerated to show that dmc catalyst activates subsequently.Behind catalyst activation, in autoclave, be metered into another part 4484.9 gram propylene oxide with the speed of 1087 stable Grams Per Hours.After being metered into totally 100 gram propylene oxide (comprising the amount that catalyst activation is used), begin to be metered into 46 gram propylene glycol (containing 750ppm water) with stable metering rate 22.75 Grams Per Hours.After being metered into totally 250 gram propylene oxide (comprising the amount that catalyst activation is used), begin to be metered into 639.6 gram glycerol (containing 2000ppm water and 75ppm phosphoric acid) with stable metering rate 177.5 Grams Per Hours.After being metered into the propylene oxide end, mixture was kept 1 hour at 130 ℃ after reaction again, with product in a vacuum, fully heated 30 minutes at 130 ℃.The maximum loop Ethylene Oxide dividing potential drop of the difference decision between the stress level that reaches when being finished by maximum reactor pressure and reaction latter stage is 1.65 crust.The OH value of product is 234.9 milligrams of KOH/ grams.
Embodiment 3
0.39 gram dmc catalyst is joined among the gram of 751 in the 10 liters of autoclaves polyvalent alcohol A.Then the material in the reactor is heated to 60 ℃, stripping 30 minutes stirs (450rpm) and logical nitrogen (50 ml/min) simultaneously.Then, with mixture heating up to 130 ℃, add 80 gram propylene oxide with the metering rate of 250 Grams Per Hours in reactor, pressure is elevated to 0.8 crust.The pressure lowering speed is accelerated to show that dmc catalyst activates subsequently.Behind catalyst activation, in autoclave, be metered into another part 4484.9 gram propylene oxide with the speed of 1087 stable Grams Per Hours.After being metered into totally 100 gram propylene oxide (comprising the amount that catalyst activation is used), begin to be metered into 46 gram propylene glycol (containing 750ppm water) with stable metering rate 22.75 Grams Per Hours.After being metered into totally 250 gram propylene oxide (comprising the amount that catalyst activation is used), begin to be metered into 640 gram glycerol (containing 2000ppm water and 75ppm phosphoric acid) with stable metering rate 177.5 Grams Per Hours.After being metered into the propylene oxide end, mixture was kept 30 minutes at 130 ℃ after reaction again, with product in a vacuum, fully heated 30 minutes at 130 ℃.The maximum loop Ethylene Oxide dividing potential drop of the difference decision between the stress level that reaches when being finished by maximum reactor pressure and reaction latter stage is 1.65 crust.The OH value of product is 235.7 milligrams of KOH/ grams.
Embodiment 4
0.39 gram dmc catalyst is joined among the gram of 752.9 in the 10 liters of autoclaves polyvalent alcohol A.Then with the material in the reactor at 20 ℃ of strippings, stir (450rpm) and logical nitrogen (50 ml/min) simultaneously.Then under 100 millibars, with the material in the reactor 20 ℃ of restir 3 hours.Then, with mixture heating up to 130 ℃, add 80 gram propylene oxide with the metering rate of 250 Grams Per Hours in reactor, pressure is elevated to 1.4 crust.The pressure lowering speed is accelerated to show that dmc catalyst activates subsequently.Behind catalyst activation, in autoclave, be metered into another part 4484.9 gram propylene oxide with the speed of 1087 stable Grams Per Hours.After being metered into totally 100 gram propylene oxide (comprising the amount that catalyst activation is used), begin to be metered into 46 gram propylene glycol (containing 750ppm water) with stable metering rate 22.75 Grams Per Hours.After being metered into totally 250 gram propylene oxide (comprising the amount that catalyst activation is used), begin to be metered into 640 gram glycerol (containing 2000ppm water and 75ppm phosphoric acid) with stable metering rate 177.5 Grams Per Hours.After being metered into the propylene oxide end, mixture was kept 40 hours at 130 ℃ after reaction again, with product in a vacuum, fully heated 30 minutes at 130 ℃.The maximum loop Ethylene Oxide dividing potential drop of the difference decision between the stress level that reaches when being finished by maximum reactor pressure and reaction latter stage is 0.95 crust.The OH value of product is 236.0 milligrams of KOH/ grams.
Embodiment 5
0.39 gram dmc catalyst is joined among the gram of 754 in the 10 liters of autoclaves polyvalent alcohol A.Then with the material in the reactor 20 ℃ of strippings 30 minutes, stir (450rpm) and logical nitrogen (50 ml/min) simultaneously.Then under 100 millibars, with the material in the reactor 20 ℃ of restir 114 minutes.Then, with mixture heating up to 130 ℃, add 80 gram propylene oxide with the metering rate of 250 Grams Per Hours in reactor, pressure is elevated to 1.7 crust.The pressure lowering speed is accelerated to show that dmc catalyst activates subsequently.Behind catalyst activation, in autoclave, be metered into another part 4484.9 gram propylene oxide with the speed of 1087 stable Grams Per Hours.After being metered into totally 100 gram propylene oxide (comprising the amount that catalyst activation is used), begin to be metered into 46.2 gram propylene glycol (containing 750ppm water) with stable metering rate 22.75 Grams Per Hours.After being metered into totally 250 gram propylene oxide (comprising the amount that catalyst activation is used), begin to be metered into 639.9 gram glycerol (containing 2000ppm water and 75ppm phosphoric acid) with stable metering rate 177.5 Grams Per Hours.After being metered into the propylene oxide end, mixture was kept 33 minutes at 130 ℃ after reaction again, with product in a vacuum, fully heated 30 minutes at 130 ℃.The maximum loop Ethylene Oxide dividing potential drop of the difference decision between the stress level that reaches when being finished by maximum reactor pressure and reaction latter stage is 1.1 crust.The OH value of product is 235.2 milligrams of KOH/ grams.
Embodiment 6 (Comparative Examples)
0.39 gram dmc catalyst is joined among the gram of 750.3 in the 10 liters of autoclaves polyvalent alcohol A.Then with the material in the reactor 130 ℃ of strippings 30 minutes, stir (450rpm) and logical nitrogen (50 ml/min) simultaneously.Then at 130 ℃, in reactor, add 80 gram propylene oxide with the metering rate of 250 Grams Per Hours.The pressure lowering speed accelerates to show that after being metered into 30 gram propylene oxide catalyzer is activated, and (peak pressure reaches: 0.5 crust).Behind catalyst activation, in autoclave, be metered into another part 4484.5 gram propylene oxide with the speed of 1087 stable Grams Per Hours.After being metered into totally 100 gram propylene oxide (comprising the amount that catalyst activation is used), begin to be metered into 46 gram propylene glycol (containing 750ppm water) with stable metering rate 22.75 Grams Per Hours.After being metered into totally 250 gram propylene oxide (comprising the amount that catalyst activation is used), begin to be metered into 639.4 gram glycerol (containing 2000ppm water and 75ppm phosphoric acid) with stable metering rate 177.5 Grams Per Hours.After being metered into the propylene oxide end, mixture was kept 30 minutes at 130 ℃ after reaction again, with product in a vacuum, fully heated 30 minutes at 130 ℃.The maximum loop Ethylene Oxide dividing potential drop of the difference decision between the stress level that reaches when being finished by maximum reactor pressure and reaction latter stage is 3.03 crust.The OH value of product is 235.6 milligrams of KOH/ grams.
Embodiment 7
0.39 gram dmc catalyst is joined among the gram of 750.6 in the 10 liters of autoclaves polyvalent alcohol A.Then with the material in the reactor 60 ℃ of strippings 30 minutes, stir (450rpm) and logical nitrogen (50 ml/min) simultaneously.Then at 60 ℃, in reactor, add 80 gram propylene oxide with the metering rate of 250 Grams Per Hours.Pressure is elevated to 0.7 crust in this process.With the material in the reactor under this pressure, 60 ℃ of restir 90 minutes.Then, with mixture heating up to 130 ℃, pressure is elevated to 2.15 crust.The pressure lowering speed is accelerated to show that dmc catalyst activates subsequently.Behind catalyst activation, in autoclave, be metered into another part 4484.9 gram propylene oxide with the speed of 1087 stable Grams Per Hours.After being metered into totally 100 gram propylene oxide (comprising the amount that catalyst activation is used), begin to be metered into 46 gram propylene glycol (containing 750ppm water) with stable metering rate 22.75 Grams Per Hours.After being metered into totally 250 gram propylene oxide (comprising the amount that catalyst activation is used), begin to be metered into 639.3 gram glycerol (containing 2000ppm water and 75ppm phosphoric acid) with stable metering rate 177.5 Grams Per Hours.After being metered into the propylene oxide end, mixture was kept 24 minutes at 130 ℃ after reaction again, with product in a vacuum, fully heated 30 minutes at 130 ℃.The maximum loop Ethylene Oxide dividing potential drop of the difference decision between the stress level that reaches when being finished by maximum reactor pressure and reaction latter stage is 1.15 crust.The OH value of product is 236.2 milligrams of KOH/ grams.
Embodiment 8 (Comparative Examples)
0.541 gram dmc catalyst is joined among the gram of 749.8 in the 10 liters of autoclaves polyvalent alcohol A.Then with the material in the reactor 130 ℃ of strippings 30 minutes, stir (450rpm) and logical nitrogen (50 ml/min) simultaneously.Then at 130 ℃, in reactor, add 80 gram propylene oxide with the metering rate of 250 Grams Per Hours.The pressure lowering speed accelerates to show that after being metered into 35 gram propylene oxide catalyzer is activated, and (peak pressure reaches: 0.65 crust).Behind catalyst activation, in autoclave, be metered into another part 4484.8 gram propylene oxide with the speed of 1087 stable Grams Per Hours.After being metered into totally 100 gram propylene oxide (comprising the amount that catalyst activation is used), begin to be metered into 46.2 gram propylene glycol (containing 750ppm water) with stable metering rate 22.75 Grams Per Hours.After being metered into totally 250 gram propylene oxide (comprising the amount that catalyst activation is used), begin to be metered into 640.0 gram glycerol (containing 1000ppm water and 75ppm phosphoric acid) with stable metering rate 177.5 Grams Per Hours.After being metered into the propylene oxide end, mixture was kept 39 minutes at 130 ℃ after reaction again, with product in a vacuum, fully heated 30 minutes at 130 ℃.The maximum loop Ethylene Oxide dividing potential drop of the difference decision between the stress level that reaches when being finished by maximum reactor pressure and reaction latter stage is 0.7 crust.The OH value of product is 235.5 milligrams of KOH/ grams.
Embodiment 9
0.37 gram dmc catalyst is joined among the gram of 749.9 in the 10 liters of autoclaves polyvalent alcohol A.Then with the material in the reactor 20 ℃ of strippings 15 minutes, stir (450rpm) and logical nitrogen (50 ml/min) simultaneously.Then, with mixture heating up to 130 ℃, add 80 gram propylene oxide with the metering rate of 250 Grams Per Hours in reactor, pressure is elevated to 2.2 crust.The pressure lowering speed is accelerated to show that dmc catalyst activates subsequently.Behind catalyst activation, in autoclave, be metered into another part 4484.8 gram propylene oxide with the speed of 1087 stable Grams Per Hours.After being metered into totally 100 gram propylene oxide (comprising the amount that catalyst activation is used), begin to be metered into 46.0 gram propylene glycol (containing 750ppm water) with stable metering rate 22.75 Grams Per Hours.After being metered into totally 250 gram propylene oxide (comprising the amount that catalyst activation is used), begin to be metered into 639.3 gram glycerol (containing 2000ppm water and 75ppm phosphoric acid) with stable metering rate 177.5 Grams Per Hours.After being metered into the propylene oxide end, mixture was kept 30 minutes at 130 ℃ after reaction again, with product at last in a vacuum, fully heated 30 minutes at 130 ℃.The maximum loop Ethylene Oxide dividing potential drop of the difference decision between the stress level that reaches when being finished by maximum reactor pressure and reaction latter stage is 1.12 crust.The OH value of product is 238.2 milligrams of KOH/ grams.
Embodiment 10
0.36 gram dmc catalyst is joined in the product of the gram of 750.1 in 10 liters of autoclaves embodiment 9.Then with the material in the reactor 20 ℃ of strippings 15 minutes, stir (450rpm) and logical nitrogen (50 ml/min) simultaneously.Then, with mixture heating up to 130 ℃, add 80 gram propylene oxide with the metering rate of 250 Grams Per Hours in reactor, pressure is elevated to 2.0 crust.The pressure lowering speed is accelerated to show that dmc catalyst activates subsequently.Behind catalyst activation, in autoclave, be metered into another part 4484.9 gram propylene oxide with the speed of 1087 stable Grams Per Hours.After being metered into totally 100 gram propylene oxide (comprising the amount that catalyst activation is used), begin to be metered into 46.1 gram propylene glycol (containing 750ppm water) with stable metering rate 22.75 Grams Per Hours.After being metered into totally 250 gram propylene oxide (comprising the amount that catalyst activation is used), begin to be metered into 639.3 gram glycerol (containing 2000ppm water and 75ppm phosphoric acid) with stable metering rate 177.5 Grams Per Hours.After being metered into the propylene oxide end, mixture was kept 40 minutes at 130 ℃ after reaction again, with product at last in a vacuum, fully heated 30 minutes at 130 ℃.The maximum loop Ethylene Oxide dividing potential drop of the difference decision between the stress level that reaches when being finished by maximum reactor pressure and reaction latter stage is 1.12 crust.The OH value of product is 235.1 milligrams of KOH/ grams.
Test parameter and the test result of embodiment 1-10 have been summed up in the Table I.
Table I
* in this embodiment, in the process in the stage of adjusting, propylene oxide joins in the reactor.
Catalyst concn in the last Table I provides with respect to end product.
Comparative Examples 8 shows that by increasing the amount and the dry glycerol of catalyzer, also can realize can be by the reaction stably of low propylene oxide dividing potential drop reflection under the situation of not using regulate process.This method is ideal of course not, because need carry out purification process before, needs to use a large amount of catalyzer.
Embodiment 11
0.24 gram dmc catalyst is joined among the gram of 300 in the 10 liters of autoclaves polyvalent alcohol C.Then with the material in the reactor 60 ℃ of strippings 30 minutes, stir (450rpm) and logical nitrogen (50 ml/min) simultaneously.Then, with the material in the reactor under 100 millibars, 60 ℃ of restir 90 minutes.Then, with mixture heating up to 130 ℃, be metered into the mixture of 3.3 gram oxyethane and 27.7 gram propylene oxide.In this process, pressure is elevated to 1.6 crust.The pressure lowering speed is accelerated to show that dmc catalyst activates subsequently.Behind catalyst activation, in autoclave, be metered into the mixture of 127.4 gram oxyethane and 1042.4 gram propylene oxide with the speed of 601.1 stable Grams Per Hours.After being metered into totally 100 gram epoxy alkane mixtures (comprising the amount that catalyst activation is used), begin to be metered into 897.7 gram polyvalent alcohol D with stable metering rate 600 Grams Per Hours.After being metered into the end of epoxy alkane mixture, mixture was kept 45 minutes at 130 ℃ after reaction again, with product at last in a vacuum, fully heated 30 minutes at 130 ℃.The maximum epoxy alkane dividing potential drop of the difference decision between the stress level that reaches when being finished by maximum reactor pressure and reaction latter stage is 1.02 crust.The OH value of product is 63.1 milligrams of KOH/ grams.
Embodiment 12 (Comparative Examples)
0.25 gram dmc catalyst is joined among the gram of 300 in the 10 liters of autoclaves polyvalent alcohol C.Then with the material in the reactor 130 ℃ of strippings 30 minutes, stir (450rpm) and logical nitrogen (50 ml/min) simultaneously.Then, be metered into the mixture of 3.3 gram oxyethane and 27.7 gram propylene oxide.In this process, pressure is elevated to 1.5 crust.The pressure lowering speed is accelerated to show that dmc catalyst activates subsequently.Behind catalyst activation, in autoclave, be metered into the mixture of 127.4 gram oxyethane and 1042.4 gram propylene oxide with the speed of 601.1 stable Grams Per Hours.After being metered into totally 100 gram epoxy alkane mixtures (comprising the amount that catalyst activation is used), begin to be metered into 897.7 gram polyvalent alcohol D with stable metering rate 600 Grams Per Hours, the pressure in the reactor is elevated to 4.2 crust rapidly.Under this pressure, to carve at this moment and be metered into 40.6 gram oxyethane and 331.5 gram propylene oxide, being metered into of epoxy alkane mixture stops.In 3 hours the process, reactor pressure drops to 3.5 crust after step of reaction, and this shows that catalyzer loses activity fully.Therefore, experiment stops.
Embodiment 13
0.24 gram dmc catalyst is joined in the product of the gram of 300.6 in 10 liters of autoclaves embodiment 9, and this product contains the 100ppm dmc catalyst that brings in its preparation.Then with the material in the reactor 60 ℃ of strippings 30 minutes, stir (450rpm) and logical nitrogen (50 ml/min) simultaneously.Then, with the material in the reactor under 100 millibars, 60 ℃ of restir 90 minutes.Then, with mixture heating up to 130 ℃, be metered into the mixture of 3.3 gram oxyethane and 27.7 gram propylene oxide.In this process, pressure is elevated to 1.3 crust.The pressure lowering speed is accelerated to show that dmc catalyst activates subsequently.Behind catalyst activation, to stablize metering rate 601 Grams Per Hours are metered into 128.9 gram oxyethane and 1042.3 gram propylene oxide in autoclave mixture.After being metered into totally 100 gram epoxy alkane mixtures (comprising the amount that catalyst activation is used), begin to be metered into 905.8 gram polyvalent alcohol D with stable metering rate 600 Grams Per Hours.After being metered into the end of epoxy alkane mixture, mixture was kept 105 minutes at 130 ℃ after reaction again, with product in a vacuum, fully heated 30 minutes at 130 ℃.The maximum epoxy alkane dividing potential drop of the difference decision between the stress level that reaches when being finished by maximum reactor pressure and reaction latter stage is 1.06 crust.The OH value of product is 63.3 milligrams of KOH/ grams.
Embodiment 14
0.24 gram dmc catalyst is joined among gram polyvalent alcohol C of 300.8 in 10 liters of autoclaves and the 898.7 gram polyvalent alcohol D.Then with the material in the reactor 60 ℃ of strippings 30 minutes, stir (450rpm) and logical nitrogen (50 ml/min) simultaneously.Then, with the material in the reactor under 100 millibars, 60 ℃ of restir 90 minutes.Then, with mixture heating up to 130 ℃, be metered into the mixture of 20.0 gram oxyethane and 100.0 gram propylene oxide.In this process, pressure is elevated to 3 crust.The pressure lowering speed is accelerated to show that dmc catalyst activates subsequently.Behind catalyst activation, to stablize metering rate 501 Grams Per Hours are metered into 112.3 gram oxyethane and 950.6 gram propylene oxide in autoclave mixture.After being metered into the end of epoxy alkane mixture, mixture was kept 40 minutes at 130 ℃ after reaction again, with product in a vacuum, fully heated 30 minutes at 130 ℃.The maximum epoxy alkane dividing potential drop of the difference decision between the stress level that reaches when being finished by maximum reactor pressure (not long ago reaching at catalyst activation in this case) and reaction latter stage is 2.4 crust.The OH value of product is 63.2 milligrams of KOH/ grams.
Test parameter and the test result of embodiment 11-14 are summarised in the Table II.
Table II
* in this embodiment, opposite with embodiment 11, before beginning to be metered into epoxide, all initial compounds all join in the reactor.
Catalyst concn in the last Table II provides with respect to end product.
Embodiment 15
0.41 gram dmc catalyst is joined among the gram of 666.6 in the 10 liters of autoclaves polyvalent alcohol B.Then the material in the reactor is heated to 60 ℃, stripping 30 minutes stirs (450rpm) and logical nitrogen (50 ml/min) simultaneously.Then, in reactor, add 66.6 gram propylene oxide at 60 ℃.Pressure is elevated to 0.6 crust in this process.Then with the material in the reactor under this pressure, 60 ℃ of restir 60 minutes.Then, with mixture heating up to 130 ℃, pressure is elevated to 1.8 crust.The pressure lowering speed is accelerated to show that dmc catalyst activates subsequently.Behind catalyst activation, in autoclave, be metered into another part 2435.7 gram propylene oxide with the speed of 648.3 stable Grams Per Hours.After being metered into totally 150 gram propylene oxide (comprising the amount that catalyst activation is used), begin to be metered into 831.2 gram propylene glycol (containing 250ppm water and 106ppm phosphoric acid) with stable metering rate 250 Grams Per Hours.After being metered into the propylene oxide end, mixture was kept 40 minutes at 130 ℃ after reaction again, with product in a vacuum, fully heated 30 minutes at 130 ℃.The maximum loop Ethylene Oxide dividing potential drop of the difference decision between the stress level that reaches when being finished by maximum reactor pressure and reaction latter stage is 1.26 crust.The OH value of product is 347.7 milligrams of KOH/ grams.
Embodiment 16 (Comparative Examples)
0.41 gram dmc catalyst is joined among the gram of 666.6 in the 10 liters of autoclaves polyvalent alcohol B.Then with the material in the reactor 130 ℃ of strippings 30 minutes, stir (450rpm) and logical nitrogen (50 ml/min) simultaneously.Then, the metering rate with 250 Grams Per Hours adds 66.6 gram propylene oxide in 60 ℃ of downhill reaction devices.In the process of the propylene oxide that is metered into this tittle, pressure is elevated to 1.5 crust immediately, and is activated at this stage D MC catalyzer, and this can be confirmed by speeding up of pressure decline.Plan is metered into another part 2436.3 gram propylene oxide with stable metering rate 648.3 Grams Per Hours in autoclave.After being metered into totally 150 gram propylene oxide (comprising the amount that catalyst activation is used), begin to be metered into 831.07 gram propylene glycol (containing 250ppm water) with stable metering rate 250 Grams Per Hours.Pressure in the reactor is elevated to 1.62 crust rapidly.Therefore, stopping ring Ethylene Oxide and propylene glycol is metered into.After 50 minutes reaction latter stage, under the pressure of 0.48 crust, begin to be metered into propylene oxide and propylene glycol with above-mentioned metering rate.Reactor pressure with than before obviously faster speed be elevated to 1.8 crust, after this, two bursts of measurement flow all stop to add.In 70 minutes reaction latter stage subsequently, pressure slowly drops to 0.8 crust.At this moment, just be metered into 469 gram propylene oxide altogether, experiment stops.
Embodiment 17
0.41 gram dmc catalyst is joined in the product of the gram of 666.0 in 10 liters of autoclaves embodiment 13, and this product contains the 103ppm dmc catalyst that brings in its preparation.Then the material in the reactor is heated to 60 ℃, stripping 30 minutes stirs (450rpm) and logical nitrogen (50 ml/min) simultaneously.Then, in reactor, add 66.6 gram propylene oxide at 60 ℃.Pressure is elevated to 0.6 crust in this process.Then with the material in the reactor under this pressure, 60 ℃ of restir 60 minutes.Then, with mixture heating up to 130 ℃, pressure is elevated to 2.0 crust.The pressure lowering speed is accelerated to show that dmc catalyst activates subsequently.Behind catalyst activation, in autoclave, be metered into another part 2474.8 gram propylene oxide with the speed of 675.5 stable Grams Per Hours.After being metered into totally 150 gram propylene oxide (comprising the amount that catalyst activation is used), begin to be metered into 792.0 gram propylene glycol (containing 280ppm water and 106ppm phosphoric acid) with stable metering rate 250 Grams Per Hours.After being metered into the propylene oxide end, mixture was kept 28 minutes at 130 ℃ after reaction again, with product at last in a vacuum, fully heated 30 minutes at 130 ℃.The maximum loop Ethylene Oxide dividing potential drop of the difference decision between the stress level that reaches when being finished by maximum reactor pressure and reaction latter stage is 1.5 crust.The OH value of product is 347.6 milligrams of KOH/ grams.
Embodiment 18
0.40 gram dmc catalyst is joined in the product of the gram of 334.9 in 10 liters of autoclaves embodiment 15, and this product contains the 120ppm dmc catalyst that brings in its preparation.Then the material in the reactor is heated to 60 ℃, stripping 30 minutes stirs (450rpm) and logical nitrogen (50 ml/min) simultaneously.Then, in reactor, add 33.3 gram propylene oxide at 60 ℃.Pressure is elevated to 0.48 crust in this process.Then with the material in the reactor under this pressure, 60 ℃ of restir 60 minutes.Then, with mixture heating up to 130 ℃, pressure is elevated to 1.2 crust.The pressure lowering speed is accelerated to show that dmc catalyst activates subsequently.Behind catalyst activation, in autoclave, be metered into another part 2763.1 gram propylene oxide with the speed of 703 stable Grams Per Hours.After being metered into totally 75 gram propylene oxide (comprising the amount that catalyst activation is used), begin to be metered into 869.9 gram propylene glycol (containing 280ppm water and 106ppm phosphoric acid) with stable metering rate 250 Grams Per Hours.After being metered into the propylene oxide end, mixture was kept 20 minutes at 130 ℃ after reaction again, with product at last in a vacuum, fully heated 30 minutes at 130 ℃.The maximum loop Ethylene Oxide dividing potential drop of the difference decision between the stress level that reaches when being finished by maximum reactor pressure and reaction latter stage is 0.85 crust.The OH value of product is 348.5 milligrams of KOH/ grams.
Test parameter and the test result of embodiment 15-18 are summarised in the Table III.
Table III
Catalyst concn in the last Table III provides with respect to end product.
Though for the purpose of illustrating, the present invention is being described in detail in the preamble, but should understand, these are described in detail only is in order to illustrate that those skilled in the art can make amendment to it under situation without departing from the spirit and scope of the present invention, and the present invention only is defined by the claims.
Claims (9)
1. method of regulating DMC catalysts, wherein double metal cyanide (DMC) catalyzer is dispersed in the starting medium, the OH value of described starting medium for 5-500 milligram KOH/ gram and comprise initial compounds with Zerewitinoff active hydrogen atom and epoxy alkane and/or poly-(ester) polyvalent alcohol and/or polycarbonate polyol and/or hydroxylated tri-glyceride 0 ℃ to 60 ℃, at 5 minutes in 4 hours, at 1 millibar of adduct to 10 pressure that cling to.
2. the method for claim 1 is characterized in that, described being adjusted under the inert gas atmosphere carried out.
3. the method for claim 1 is characterized in that, described being adjusted under the atmosphere that contains rare gas element and epoxy alkane carried out.
4. one kind adds the method that initial compounds and epoxy alkane prepare polyether glycol by continuous measurement, comprises the dmc catalyst of regulating according to claim 1.
5. continuous production method that adds initial compounds, epoxy alkane by continuous measurement and prepare polyether glycol as the dmc catalyst of adjusting as described in the claim 2.
6. method for preparing polyether glycol comprises the dmc catalyst of regulating according to claim 1, and the initial compounds of whole amounts that wherein is used for preparing polyether glycol is in the dmc catalyst regulate process Already in the starting medium.
7. in a kind of method for preparing polyurethane material, its improvement comprises: comprise the polyether glycol by method preparation as claimed in claim 4.
8. in a kind of method for preparing polyurethane material, its improvement comprises: comprise the polyether glycol by method preparation as claimed in claim 5.
9. in a kind of method for preparing polyurethane material, its improvement comprises: the polyether glycol that comprises method preparation as claimed in claim 6.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102006024025.1 | 2006-05-23 | ||
| DE102006024025A DE102006024025A1 (en) | 2006-05-23 | 2006-05-23 | Process for the preparation of polyether polyols |
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| Publication Number | Publication Date |
|---|---|
| CN101077964A CN101077964A (en) | 2007-11-28 |
| CN101077964B true CN101077964B (en) | 2011-08-03 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2007101040858A Expired - Fee Related CN101077964B (en) | 2006-05-23 | 2007-05-22 | method for producing polyether polyols |
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|---|---|
| US (2) | US7678729B2 (en) |
| EP (1) | EP1859863A3 (en) |
| JP (1) | JP2007314787A (en) |
| KR (1) | KR101378232B1 (en) |
| CN (1) | CN101077964B (en) |
| BR (1) | BRPI0701656A (en) |
| CA (1) | CA2588898A1 (en) |
| DE (1) | DE102006024025A1 (en) |
| MX (1) | MX2007006078A (en) |
| SG (1) | SG137810A1 (en) |
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|---|---|---|---|---|
| US20080021191A1 (en) * | 2006-07-20 | 2008-01-24 | Reese Jack R | High water content tolerant process for the production of polyethers |
| DE102008011683A1 (en) * | 2008-02-28 | 2009-09-03 | Bayer Materialscience Ag | Process for the preparation of polyols |
| CN102282189A (en) * | 2008-11-14 | 2011-12-14 | 陶氏环球技术有限责任公司 | Modified natural oils and products made therefrom |
| CN102574999A (en) * | 2009-09-17 | 2012-07-11 | 旭硝子株式会社 | Polyether preparation method |
| KR20120080597A (en) | 2009-10-05 | 2012-07-17 | 아사히 가라스 가부시키가이샤 | Polyethers and method for producing the same |
| EP2490805B1 (en) * | 2009-10-19 | 2019-05-01 | Basf Se | Conditioning of double metal cyanide catalysts |
| US8461285B2 (en) * | 2010-03-09 | 2013-06-11 | Basf Se | Process for preparing polyether polyols |
| US20110230581A1 (en) * | 2010-03-17 | 2011-09-22 | Bayer Materialscience Llc | Process for the production of polyether polyols with a high ethylene oxide content |
| ES2587257T3 (en) * | 2010-03-24 | 2016-10-21 | Covestro Deutschland Ag | Procedure for the preparation of polyolethercarbonates |
| DE102010043409A1 (en) | 2010-11-04 | 2012-05-10 | Bayer Materialscience Aktiengesellschaft | Process for the preparation of polycarbonate polyols by immortal polymerization of cyclic carbonates |
| BR112014015221A2 (en) | 2011-12-20 | 2017-06-13 | Bayer Intellectual Property Gmbh | hydroxyamino polymers and processes for their preparation |
| CN103910864B (en) * | 2013-01-09 | 2016-12-28 | 万华化学集团股份有限公司 | A kind of preparation method of the block oligomeric diols of structure-controllable |
| SG2014014567A (en) * | 2013-02-22 | 2014-09-26 | Bayer Materialscience Ag | Process for preparing polyether polyols |
| MX337785B (en) * | 2013-02-22 | 2016-03-18 | Bayer Materialscience Ag | Process for preparing polyether polyols. |
| EP2865700A1 (en) * | 2013-10-23 | 2015-04-29 | Bayer MaterialScience AG | Method for manufacturing polyether carbonate polyols |
| ES2730113T3 (en) | 2015-07-02 | 2019-11-08 | Covestro Llc | Process for the preparation of a poly (ether polyol) using a DMC catalyst and continuous addition of an initiator |
| WO2017032768A1 (en) * | 2015-08-26 | 2017-03-02 | Covestro Deutschland Ag | Method for producing high molecular weight polyoxyalkylene polyols |
| EP3138865A1 (en) * | 2015-09-07 | 2017-03-08 | Basf Se | Method for manufacturing polyether polyols |
| CN110964191B (en) * | 2018-09-29 | 2021-02-02 | 杭州普力材料科技有限公司 | Mixed acid modified zinc-cobalt double metal cyanide catalyst and preparation method thereof |
| WO2023216101A1 (en) * | 2022-05-10 | 2023-11-16 | 宁德时代新能源科技股份有限公司 | Positive electrode slurry, positive electrode sheet, and secondary battery comprising positive electrode sheet |
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Also Published As
| Publication number | Publication date |
|---|---|
| MX2007006078A (en) | 2009-02-16 |
| BRPI0701656A (en) | 2008-01-15 |
| KR101378232B1 (en) | 2014-03-27 |
| JP2007314787A (en) | 2007-12-06 |
| EP1859863A3 (en) | 2008-07-23 |
| US7772330B2 (en) | 2010-08-10 |
| US20100125126A1 (en) | 2010-05-20 |
| US20070276099A1 (en) | 2007-11-29 |
| DE102006024025A1 (en) | 2007-11-29 |
| CN101077964A (en) | 2007-11-28 |
| US7678729B2 (en) | 2010-03-16 |
| KR20070113141A (en) | 2007-11-28 |
| EP1859863A2 (en) | 2007-11-28 |
| SG137810A1 (en) | 2007-12-28 |
| CA2588898A1 (en) | 2007-11-23 |
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